无机材料学报 ›› 2020, Vol. 35 ›› Issue (12): 1315-1326.DOI: 10.15541/jim20200096
所属专题: 封面文章
收稿日期:
2020-02-29
修回日期:
2020-04-09
出版日期:
2020-12-20
网络出版日期:
2020-05-20
作者简介:
高 天(1992–), 男, 博士. E-mail: 1217387634@qq.com
基金资助:
GAO Tian(),XIAO Qinglin,XU Chenyang,WANG Xuebin(
)
Received:
2020-02-29
Revised:
2020-04-09
Published:
2020-12-20
Online:
2020-05-20
About author:
GAO Tian(1992–), male, PhD. E-mail: 1217387634@qq.com
Supported by:
摘要:
以石墨烯为代表的二维材料具有优异的本征性质, 例如高表面积和电导率, 但其宏观块体材料的性质仍不理想。这是由于石墨烯片层堆叠损失了有效的表面; 片层之间联结较弱导致接触电阻和热阻增大。原则上二维材料的三维化设计能避免上述问题, 将纳米尺度的优异性质传递到宏观尺度, 获得高表面积、高导电、贯通孔道和优良机械性能的块体材料。二维材料多孔块体可用于电极、吸附剂和弹性体等。发泡法工艺简单、成本低, 是近年来制备二维材料泡沫体的主要方法。本文系统总结了发泡法的基本原理, 综述了石墨烯、氮化硼等二维材料泡沫体的研究进展, 展望了二维材料泡沫体在能源、环境等方面的应用前景。
中图分类号:
高天, 肖庆林, 许晨阳, 王学斌. 发泡法制备二维材料泡沫体的进展[J]. 无机材料学报, 2020, 35(12): 1315-1326.
GAO Tian, XIAO Qinglin, XU Chenyang, WANG Xuebin. Blowing Route to Fabricate Foams of 2D Materials[J]. Journal of Inorganic Materials, 2020, 35(12): 1315-1326.
图1 多种维度的sp2杂化碳纳米材料, 石墨烯粉体、薄膜和块体三种形态, 以及设计三维石墨烯的理念
Fig. 1 Different-dimensional sp2-hybrid carbon nanomaterials, graphene forms (powder, film, and monolith), and concept of 3D graphene
图3 堆砌的(a)Kelvin结构和(b)Weaire-Phelan结构; (c)发泡动力学示意图
Fig. 3 (a) Kelvin structure and (b) Weaire-Phelan structure for honeycomb, (c) scheme of blowing kinetics
图5 (a)化学发泡法示意图; (b, c)SG实物和光学图像; (d)SG中石墨烯壁和石墨筋的光学图像; (e, f)中间体聚合物泡沫及其泡壁的SEM照片; (g)纯化后的石墨烯片层的光学照片; (h)石墨烯片层的AFM图像; (i)SG的HRTEM照片; (j~m)分别以1、4、20、100 ℃/min加热发泡得到的不同SG的SEM照片[24,55]
Fig. 5 (a) Scheme of chemical blowing process; (b, c) Photo and optical image of SG; (d) Optical image of a graphene membrane and graphitic struts of SG; (e, f) Scanning electron microscope (SEM) images of intermediate polymeric bubbles and their thin walls; (g) Optical image of a large few-layered graphene membrane taken from SG; (h) Atomic force microscope (AFM) image of an individual graphene membrane; (i) High-resolution transmission electron microscope (HRTEM) images of SG; (j-m) SEM images of strutted graphene grown at heating rates of 1, 4, 20 and 100 ℃/min[24,55]
Precursor | Blowing agent | Heteroatom source | Temperature /℃ | Product | SSA /(m2?g-1) | Application | Ref. |
---|---|---|---|---|---|---|---|
Glucose | NH4Cl | - | 1350 | Strutted graphene (SG) | 1005 | Supercapacitor | [ |
Sugar | NH4Cl | - | 1400 | Strutted graphene (SG) | 710 | Supercapacitor | [ |
Glucose | NH4Cl | - | 1000 | 3D carbon materials (CMs) | 170 | Li metal battery | [ |
Glucose | (NH4)2CO3, citric acid | (NH4)2CO3 | 900 | N-doped 3D mesoporous foam | 516 | Electrocatalysis Thermocatalysis | [ |
Glucose | NH4Cl, melamine | Melamine | 1100 | 3D N-doped graphene (3DNG) layers | 1190 | Supercapacitor | [ |
Starch | Urea | Urea | 800 | N-doped graphitized carbon nanosheets | 1947 | Supercapacitor | [ |
PMP | Melamine | Melamine, H3PO4 | 1050 | N-P-O co-doped monolith carbon aerogel | 2668 | Supercapacitor Adsorption | [ |
Glucose | Melamine | Melamine, H3PO4 | 1050 | P/N co-doped functional exfoliated carbon | 1440 | Electrocatalysis | [ |
Chitosan | NH4Cl | NH4Cl | 900 | 3D hierarchically porous N-doped carbon | 1005 | Electrocatalysis | [ |
Citric acid | NH4Cl | NH4Cl | 1000 | Hierarchically interconnected N-doped carbon nanosheets (NCNS) | 1460 | Electrocatalysis | [ |
表1 采用发泡法制备的石墨烯泡沫体和掺杂石墨烯泡沫体(使用无残留的铵盐发泡剂)
Table 1 Graphene foams and doped graphene foams fabricated via blowing route using residue-free ammonium blowing agents
Precursor | Blowing agent | Heteroatom source | Temperature /℃ | Product | SSA /(m2?g-1) | Application | Ref. |
---|---|---|---|---|---|---|---|
Glucose | NH4Cl | - | 1350 | Strutted graphene (SG) | 1005 | Supercapacitor | [ |
Sugar | NH4Cl | - | 1400 | Strutted graphene (SG) | 710 | Supercapacitor | [ |
Glucose | NH4Cl | - | 1000 | 3D carbon materials (CMs) | 170 | Li metal battery | [ |
Glucose | (NH4)2CO3, citric acid | (NH4)2CO3 | 900 | N-doped 3D mesoporous foam | 516 | Electrocatalysis Thermocatalysis | [ |
Glucose | NH4Cl, melamine | Melamine | 1100 | 3D N-doped graphene (3DNG) layers | 1190 | Supercapacitor | [ |
Starch | Urea | Urea | 800 | N-doped graphitized carbon nanosheets | 1947 | Supercapacitor | [ |
PMP | Melamine | Melamine, H3PO4 | 1050 | N-P-O co-doped monolith carbon aerogel | 2668 | Supercapacitor Adsorption | [ |
Glucose | Melamine | Melamine, H3PO4 | 1050 | P/N co-doped functional exfoliated carbon | 1440 | Electrocatalysis | [ |
Chitosan | NH4Cl | NH4Cl | 900 | 3D hierarchically porous N-doped carbon | 1005 | Electrocatalysis | [ |
Citric acid | NH4Cl | NH4Cl | 1000 | Hierarchically interconnected N-doped carbon nanosheets (NCNS) | 1460 | Electrocatalysis | [ |
图6 (a)以三聚氰胺发泡PMP过程示意图; (b)N-P-O共掺杂石墨烯泡沫体的SEM照片[67]
Fig. 6 (a) Synthesis scheme of foaming based on PMP precursor; (b) SEM images of N-P-O-co-doped graphene foam[67]
图7 担载型石墨烯泡沫体制备示意图及其SEM/HRTEM照片
Fig. 7 Synthesis schemes and SEM/HRTEM images of loaded graphene foam (a, b) Fe2O3[35]; (c, d) Co2P[36]; (e, g) NiFeP[73]
Precursor | Blowing agent of salt | Temperature /℃ | Product | SSA /(m2?g-1) | Application | Ref. |
---|---|---|---|---|---|---|
Glucose | Fe(NO3)3 | 950 | Graphene-like carbon nanosheets (GCNs) | 220 | Electrosorption | [ |
Sucrose | Zn(NO3)2 | 1200 | Foam-like porous carbon | 2340 | Supercapacitor | [ |
Hydrolyzed starch | ZnCl2 | 400 | Activated carbon foam with nano-thickness cell walls (ACF-NCW) | 926 | Supercapacitor | [ |
Cellulose | KHCO3 | 400 | Hierarchically porous carbons (HPCs) | 1893 | Supercapacitor | [ |
Maltose | Ni(NO3)2 | 800 | Macroporous graphitic carbon foam (MGCF) | 804 | Microbial fuel cell | [ |
Sucrose | Ni(NO3)2 | 900 | Carbon-graphite composite foam | — | Heat dissipation | [ |
Maltose | Co(NO3)2 | 900 | Graphene-like carbon nanosheets (GCNs) | 735 | Electrosorption | [ |
Potassium citrate | C6H5K3O7 | 850 | Porous carbon nanosheets (PCNs) | 2200 | Supercapacitor | [ |
Acrylic-type cation-exchange resin | Ni(CH3COO)2 | 850 | 3D hierarchical porous graphene-like network | 1411 | Li ion battery | [ |
Artemia cyst shells | Ni(CH3COO)2 | 850 | N-P-O co-doped 3D graphene | 1406 | Supercapacitor Electrocatalysis | [ |
Glucose | Zn(NO3)2 | 800 | N-doped holey graphene | 1602 | Supercapacitor | [ |
Poly-o- phenylenediamine | Ni(NO3)2 | 900 | 3D N-doped graphene (3DNGN) | 907 | Supercapacitor | [ |
Coal tar pitch | Mg(CH3COO)2 | 700 | O/N co-doped foam-like porous carbon | 1010 | Supercapacitor | [ |
EDTA, EG | Ni(NO3)2 | 550 | 3D N-doped carbon nanosheet@carbon nanotube (NCNS@CNT) | 375 | Supercapacitor | [ |
PVP | Fe(NO3)3 | 700 | 3D N-doped carbon nanosheet frameworks decorated with Fe2O3 nanoparticles (Fe2O3-NCNF) | 306 | Li ion battery | [ |
Glucose | Co(NO3)2 | 900 | CoO@Co/N-doped carbon (CoO@Co/N-C) | 551 | Electrocatalysis | [ |
Glucose | Sb(CH3COO)3, NH4Cl | 950 | Sb/C composite material | — | Na ion battery | [ |
Glucose | (NH4)2MoS4, NH4Cl | 1000 | MoS2/3D graphene structure (MoS2-G) | — | Electrocatalysis | [ |
PVP | Fe(NO3)3 | 800 | 3D foam-like graphenic carbon scaffold incorporated with FeP nanoparticles (FeP@FGCS) | 159 | K ion battery | [ |
PVP | Fe(NO3)3 | 900 | FexO nanospheres anchored on 3D N-doped few-layer graphene framework (FexO@NFLG) | 239 | K ion battery | [ |
PVP | Fe(NO3)3 | 750 | 3D N-doped graphenic framework coupled with Fe3C@porous graphite carbon core-shell structures (Fe3C@PGC-NGF) | 238 | K ion battery | [ |
Glucose | CuCl2, NH4Cl | 900 | Cu/graphene composite | — | Catalysis | [ |
Glucose | CrCl3 | 1050 | Cr6+@graphene | — | Electrocatalysis | [ |
Gelatin | Fe(NO3)3 | 500 | Fe2O3@N-doped carbon foam | 418 | Supercapacitor Li ion battery | [ |
Polydopamine | Co(NO3)2 | 900 | Metal and nitrogen co-doped carbon (M/N-C) | 276 | Electrocatalysis | [ |
Wheat flour | Co(NO3)2 | 800 | N,S- doped hierarchically porous carbon with core-shell Co@C nanoparticles (Co-N-S-PC) | 734 | Catalysis | [ |
Glucose | Ni(NO3)2 | 650 | Graphene-like foam/NiO composite (GLF/NiO) | 323 | Supercapacitor | [ |
表2 采用发泡法制备石墨烯泡沫体和担载型石墨烯泡沫体(使用含金属元素的盐类作为发泡剂)
Table 2 Pristine and loaded graphene foams fabricated via blowing route using metal-contained salt blowing agents
Precursor | Blowing agent of salt | Temperature /℃ | Product | SSA /(m2?g-1) | Application | Ref. |
---|---|---|---|---|---|---|
Glucose | Fe(NO3)3 | 950 | Graphene-like carbon nanosheets (GCNs) | 220 | Electrosorption | [ |
Sucrose | Zn(NO3)2 | 1200 | Foam-like porous carbon | 2340 | Supercapacitor | [ |
Hydrolyzed starch | ZnCl2 | 400 | Activated carbon foam with nano-thickness cell walls (ACF-NCW) | 926 | Supercapacitor | [ |
Cellulose | KHCO3 | 400 | Hierarchically porous carbons (HPCs) | 1893 | Supercapacitor | [ |
Maltose | Ni(NO3)2 | 800 | Macroporous graphitic carbon foam (MGCF) | 804 | Microbial fuel cell | [ |
Sucrose | Ni(NO3)2 | 900 | Carbon-graphite composite foam | — | Heat dissipation | [ |
Maltose | Co(NO3)2 | 900 | Graphene-like carbon nanosheets (GCNs) | 735 | Electrosorption | [ |
Potassium citrate | C6H5K3O7 | 850 | Porous carbon nanosheets (PCNs) | 2200 | Supercapacitor | [ |
Acrylic-type cation-exchange resin | Ni(CH3COO)2 | 850 | 3D hierarchical porous graphene-like network | 1411 | Li ion battery | [ |
Artemia cyst shells | Ni(CH3COO)2 | 850 | N-P-O co-doped 3D graphene | 1406 | Supercapacitor Electrocatalysis | [ |
Glucose | Zn(NO3)2 | 800 | N-doped holey graphene | 1602 | Supercapacitor | [ |
Poly-o- phenylenediamine | Ni(NO3)2 | 900 | 3D N-doped graphene (3DNGN) | 907 | Supercapacitor | [ |
Coal tar pitch | Mg(CH3COO)2 | 700 | O/N co-doped foam-like porous carbon | 1010 | Supercapacitor | [ |
EDTA, EG | Ni(NO3)2 | 550 | 3D N-doped carbon nanosheet@carbon nanotube (NCNS@CNT) | 375 | Supercapacitor | [ |
PVP | Fe(NO3)3 | 700 | 3D N-doped carbon nanosheet frameworks decorated with Fe2O3 nanoparticles (Fe2O3-NCNF) | 306 | Li ion battery | [ |
Glucose | Co(NO3)2 | 900 | CoO@Co/N-doped carbon (CoO@Co/N-C) | 551 | Electrocatalysis | [ |
Glucose | Sb(CH3COO)3, NH4Cl | 950 | Sb/C composite material | — | Na ion battery | [ |
Glucose | (NH4)2MoS4, NH4Cl | 1000 | MoS2/3D graphene structure (MoS2-G) | — | Electrocatalysis | [ |
PVP | Fe(NO3)3 | 800 | 3D foam-like graphenic carbon scaffold incorporated with FeP nanoparticles (FeP@FGCS) | 159 | K ion battery | [ |
PVP | Fe(NO3)3 | 900 | FexO nanospheres anchored on 3D N-doped few-layer graphene framework (FexO@NFLG) | 239 | K ion battery | [ |
PVP | Fe(NO3)3 | 750 | 3D N-doped graphenic framework coupled with Fe3C@porous graphite carbon core-shell structures (Fe3C@PGC-NGF) | 238 | K ion battery | [ |
Glucose | CuCl2, NH4Cl | 900 | Cu/graphene composite | — | Catalysis | [ |
Glucose | CrCl3 | 1050 | Cr6+@graphene | — | Electrocatalysis | [ |
Gelatin | Fe(NO3)3 | 500 | Fe2O3@N-doped carbon foam | 418 | Supercapacitor Li ion battery | [ |
Polydopamine | Co(NO3)2 | 900 | Metal and nitrogen co-doped carbon (M/N-C) | 276 | Electrocatalysis | [ |
Wheat flour | Co(NO3)2 | 800 | N,S- doped hierarchically porous carbon with core-shell Co@C nanoparticles (Co-N-S-PC) | 734 | Catalysis | [ |
Glucose | Ni(NO3)2 | 650 | Graphene-like foam/NiO composite (GLF/NiO) | 323 | Supercapacitor | [ |
图8 g-C3N4泡沫体的(a)合成示意图及(b~d)不同加热速率下发泡所获得样品的TEM照片[87]
Fig. 8 (a) Synthesis scheme and (b-d) TEM images of 3D strutted g-C3N4 foam heated at different rates[87]
图9 氨硼烷(AB)自发泡法制备BN泡沫体: (a)示意图, (b)SEM照片, (c)光学照片, (d)AFM和HRTEM图像[29]; 硼酸-PEO体系发泡制备BN泡沫体: (f)示意图, (g, h)SEM照片[97]
Fig. 9 (a) Synthesis scheme, (b) SEM, (c) optical, (d) AFM and (e) HRTEM images of BN foam by foaming of AB[29]; (f) Synthesis scheme and (g, h) SEM images of BN foam using boric acid and PEO[97]
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